Fungicidal mixtures

ABSTRACT

Fungicidal mixtures, comprising 
 
A) the triazolopyrimidine of the formula I  
                 
and 
 
B) amide compounds of the formula II  
                 
         where X 1  and X 2  are halogen, nitro, cyano, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, haloalkylthio, alkylsulfinyl or alkylsulfonyl; x is 1, 2, 3 or 4; and y is 1, 2, 3, 4 or 5; in a synergistically effective amount, methods for controlling harmful fungi using mixtures of the compounds I and II, compositions comprising these compounds and the use of the compounds I and II for preparing such mixtures are described.

The present invention relates to fungicidal mixtures comprising

-   -   A) the triazolopyrimidine of the formula I        and    -   B) amide compounds of the formula II    -   where X¹ and X² are identical or different and are halogen,        nitro, cyano, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl,        C₁-C₈-haloalkyl, C₂-C₈-haloalkenyl, C₂-C₈-haloalkynyl,        C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, C₁-C₈-haloalkylthio,        C₁-C₈-alkylsulfinyl or C₁-C₈-alkylsulfonyl;    -   x is 1, 2, 3 or 4; and    -   y is 1, 2, 3, 4 or 5;        in a synergistically effective amount.

Moreover, the invention relates to methods for controlling harmful fungiusing mixtures of the compounds I and II, to compositions comprisingthese mixtures and to the use of the compounds I and II for preparingsuch mixtures.

The compound of the formula I,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,its preparation and its action against harmful fungi are known from theliterature (WO 98/46607).

Mixtures of triazolopyrimidines with other active compounds aregenerally known from EP-A 988 790 and U.S. Pat. No. 6,268,371.

Also known are the amide compounds of the formula II, their preparationand their action against harmful fungi (EP-A 545 099).

Mixtures of the amide compounds of the formula II with other activecompounds are also known (WO 97/10716, WO 97/39628, WO 99/31981).

It is an object of the present invention to provide further particularlyeffective mixtures for controlling harmful fungi and in particular forcertain indications. With a view to reducing the application rates andto improving the activity spectrum of the known compounds I and II, itwas an object of the present invention to provide mixtures which, withreduced total amount of active compounds applied, have improved actionagainst harmful fungi (synergistic mixtures).

We have found that this object is achieved by the mixtures defined atthe outset. Moreover, it has been found that simultaneous, that is jointor separate, application of the compounds I and the compounds II orsuccessive application of the compounds I and the compounds II allowsbetter control of harmful fungi than is possible with the individualcompounds alone.

The mixtures according to the invention have synergistic action and aretherefore suitable for controlling harmful fungi and in particularpowdery mildew fungi in cereals, vegetables, fruit, ornamental plantsand grapevines.

The formula II represents in particular compounds in which X¹ is locatedin the 2-position and X² is located in the 4-position (formula II.1):

Preference is given to compounds of the formula II.1 in which thecombination of the substituents corresponds to one row of Table 2 below:No. X¹ X² II-1 F F II-2 F Cl II-3 F Br II-4 Cl F II-5 Cl Cl II-6 Cl BrII-7 CF₃ F II-8 CF₃ Cl II-9 CF₃ Br II-10 CF₂H F II-11 CF₂H Cl II-12 CF₂HBr II-13 CH₃ F II-14 CH₃ Cl II-15 CH₃ Br II-16 OCH₃ F II-17 OCH₃ ClII-18 OCH₃ Br II-19 SCH₃ F II-20 SCH₃ Cl II-21 SCH₃ Br II-22 S(O)CH₃ FII-23 S(O)CH₃ Cl II-24 S(O)CH₃ Br II-25 SO₂CH₃ F II-26 SO₂CH₃ Cl II-27SO₂CH₃ Br

Particular preference is given to compounds II.1 in which X¹ is CF₃ orhalogen and X² is halogen, in particular to the compound II-5 (commonname: boscalid).

When preparing the mixtures, it is preferred to employ the pure activecompounds I and II, to which further compounds active against harmfulfungi or other pests, such as insects, arachnids or nematodes, or elseherbicidal or growth-regulating active ingredients or fertilizers can beadded.

The mixtures of the compounds I and II, or the compounds I and II usedsimultaneously, together or separately, exhibit outstanding activityagainst a wide range of phytopathogenic fungi, in particular from theclasses of the Ascomycetes, Deuteromycetes, Phycomycetes andBasidiomycetes. Some of them act systemically and can therefore also beemployed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as bananas, cotton, vegetable species(for example cucumbers, beans and cucurbits), barley, grass, oats,coffee, potatoes, corn, fruit species, rice, rye, soybean, tomatoes,grapevine, wheat, ornamentals, sugar cane, and a multiplicity of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Blumeria graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugar cane, Venturia inaequalisin apples, Bipolaris and Drechslera species in cereals, rice and lawnsSeptoria nodorum in wheat, Botrytis cinera in strawberries, vegetables,ornamentals and grapevines, Mycosphaerella species in bananas,groundnuts and cereals, Pseudocercosporella herpotrichoides in wheat andbarley, Pyricularia oryzae in rice, Phytophthora infestans in potatoesand tomatoes, Pseudoperonospora species in cucurbits and hops,Plasmopara viticola in grapevines, Alternaria species in vegetables andfruit and also Fusarium and Verticillium species.

Moreover, they can be used in the proteection of materials (for examplethe protection of wood), for example against Paecilomyces variotii.

The compounds I and II can be applied simultaneously, that is togetheror separately, or in succession, and the sequence here, in the case ofseparate application, does not generally have any effect on the resultof the control measures.

The compounds I and II are usually applied in a weight ratio of from100:1 to 1:100, in particular from 20:1 to 1:20, preferably from 20:1 to1:5.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are, in particular in agriculturalcrop areas, from 5 to 2000 g/ha, preferably from 50 to 1500 g/ha, inparticular from 50 to 750 g/ha.

The application rates here of the compounds I are from 5 to 2000 g/ha,preferably from 50 to 1500 g/ha, in particular from 5 to 750 g/ha.

Correspondingly, in the case of the compounds II, the application ratesare from 5 to 2000 g/ha, preferably from 50 to 1500 kg/ha, in particularfrom 50 to 750 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 1 g/kg of seed, preferably from 0.01 to 0.5 g/kg, inparticular from 0.01 to 0.1 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II or of the mixtures of thecompounds I and II is effected by spraying or dusting the seeds, theplants or the soils before or after sowing of the plants, or before orafter plant emergence.

The mixtures according to the invention or the compounds I and II can beconverted into the customary formulations, for example solutions,emulsions, suspensions, dusts, powders, pastes and granules. Theapplication form depends on the particular purpose; in each case, itshould ensure a fine and uniform distribution of the compound accordingto the invention.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants. Solvents/auxiliaries which aresuitable are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethylamides, fatty acids and fatty acid esters. In        principle, solvent mixtures may also be used.    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        highly disperse silica, silicates); emulsifiers such as nonionic        and anionic emulsifiers (for example polyoxyethylene fatty        alcohol ethers, alkylsulfonates and arylsulfonates) and        dispersants such as lignin-sulfite waste liquors and        methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andsulfated fatty alcohol glycol ethers, furthermore condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acid with phenoland formaldehyde, polyoxyethylene octylphenyl ether, ethoxylatedisooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers,tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxidecondensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal,sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. Theactive compounds are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:

1. Products for Dilution with Water

A) Soluble Concentrates (SL)

10 parts by weight of the active compounds are dissolved in water or ina water-soluble solvent. As an alternative, wetters or other auxiliariesare added. The active compound dissolves upon dilution with water.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved incyclohexanone with addition of a dispersant, for examplepolyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). Dilution with water gives an emulsion.

D) Emulsions (EW, EO)

40 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). This mixture is introduced into water bymeans of an emulsifier (Ultraturax) and made into a homogeneousemulsion. Dilution with water gives an emulsion.

E) Suspensions (SC, OD)

In an agitated ball mill, 20 parts by weight of the active compounds arecomminuted with addition of dispersants, wetters and water or an organicsolvent to give a fine active compound suspension. Dilution with watergives a stable suspension of the active compound.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compounds are ground finely withaddition of dispersants and wetters and made into water-dispersible orwater-soluble granules by means of technical appliances (for exampleextrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active compound.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP)

75 parts by weight of the active compounds are ground in a rotor-statormill with addition of dispersants, wetters and silica gel. Dilution withwater gives a stable dispersion or solution with the active compound.

2. Products to be Applied Undiluted

H) Dustable Powders (DP)

5 parts by weight of the active compounds are ground finely and mixedintimately with 95% of finely divided kaolin. This gives a dustableproduct.

I) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compounds is ground finely andassociated with 95.5% carriers. Current methods are extrusion,spray-drying or the fluidized bed. This gives granules to be appliedundiluted.

J) ULV Solutions (UL)

10 parts by weight of the active compounds are dissolved in an organicsolvent, for example xylene. This gives a product to be appliedundiluted.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; it is intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, ifappropriate just immediately prior to use (tank mix). These agents canbe admixed with the agents according to the invention in a weight ratioof 1:10 to 10:1.

The compounds I and II or the mixtures or the corresponding formulationsare applied by treating the harmful fungi or the plants, seeds, soils,areas, materials or spaces to be kept free from them with a fungicidallyeffective amount of the mixture or, in the case of separate application,of the compounds I and II. Application can be carried out before orafter infection by the harmful fungi.

The fungicidal action of the compound and the mixtures can bedemonstrated by the experiments below:

The active compounds, separately or jointly, were prepared as a stocksolution with 0.25% by weight of active compound in acetone or DMSO. 1%by weight of the emulsifier UniperolR EL (wetting agent havingemulsifying and dispersing action based on ethoxylated alkylphenols) wasadded to this solution, and the solution was diluted with water to thedesired concentration.

USE EXAMPLE 1 Curative Activity Against Wheat Leaf Rust Caused byPuccinia recondita

Leaves of potted wheat seedlings of the cultivar “Kanzler” were dustedwith spores of leaf rust (Puccinia recondita). For 24 hours, the potswere then placed at 20-22_C in a chamber with high atmospheric humidity(90-95%). During this time, the spores germinated and the germinal tubespenetrated into the leaf tissue. The next day, the infected plants weresprayed to runoff point with an aqueous suspension having theconcentration of active compounds stated below. The suspension oremulsion was prepared as described above. After the spray coating haddried on, the test plants were cultivated in a greenhouse at 20-22_C and65-70% relative atmospheric humidity for 7 days. The extent of rustfungus development on the leaves was then determined.

Evaluation was carried out by determining the infected leaf areas as apercentage. These percentages were converted into efficacies. Theefficacy (W) was calculated as follows using Abbot's formula:W=(1−a/b)·100

-   -   a corresponds to the fungal infection of the treated plants in %        and    -   b corresponds to the fungal infection of the untreated (control)        plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of the active compounds weredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.Colby's formula: E=x+y−x·y/100

-   -   E expected efficacy, expressed as % of the untreated control,        when using the mixture of the active compounds A and B at the        concentrations a and b    -   x efficacy, expressed as % of the untreated control, when using        active compound A at a concentration a

y efficacy, expressed as % of the untreated control, when using activecompound B at a concentration b TABLE A Individual active compoundsConcentration of active compound in Efficacy in % of the spray liquorthe untreated Example Active compound [ppm] control 1 Control (90%infection) (untreated) 2 I 4 56 1 0 3 II-5 (boscalid) 4 0 0.25 0

TABLE B Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 4 I + II-5 92 56 4 + 0.25 ppm 16:1 5 I + II-5 92 56 4 + 4 ppm 1:1 6 I + II-5 33  0 1 + 4 ppm  1:4*)efficacy calculated using Colby's formula

USE EXAMPLE 2 Activity Against Gray Mold on Bellpepper Leaves Caused byBotrytis cinerea, Protective Application

Bellpepper seedlings of the cultivar “Neusiedler Ideal Elite” were,after 4-5 leaves were well developed, sprayed to runoff point with anaqueous suspension having the active compound concentration statedbelow. The next day, the treated plants were inoculated with a sporesuspension of Botrytis cinerea which contained 1.7×10⁶ spores/ml in a 2%strength aqueous biomalt solution. The test plants were then placed in aclimatized chamber at 22-24_C and high atmospheric humidity. After 5days, the extent of the fungus development on the leaves could bedetermined visually in %.

Evaluation was carried out analogously to example 1. TABLE C Individualactive compounds Concentration of active compound in Efficacy in % ofthe spray liquor the untreated Example Active compound [ppm] control 7Control (95% infection) (untreated) 8 I 4 68 1 37 0.25 0 9 II-5(boscalid) 1 0 0.25 0

TABLE D Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 10 I + II-5 95 68 4 + 0.25 ppm 16:1 11 I + II-5 100 37 1 + 1ppm  1:1 12 I + II-5 79 0 0.25 + 0.25 ppm  1:1 13 I + II-5 89 0 0.25 + 1ppm  1:4*)efficacy calculated using Colby's formula

The test results show that in all mixing ratios the efficacy observedfor the combinations according to the invention is higher than thatcalculated beforehand using Colby's formula.

1. A fungicidal mixture, comprising A) the triazolopyrimidine of theformula I,

and B) amide compounds of the formula II

where X¹ and X² are identical or different and are halogen, nitro,cyano, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₈-haloalkyl,C₂-C₈-haloalkenyl, C₂-C₈-haloalkynyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy,C₁-C₈-haloalkylthio, C₁-C₈-alkylsulfinyl or C₁-C₈-alkylsulfonyl; x is 1,2, 3 or 4; and y is 1, 2, 3, 4 or 5; in a synergistically effectiveamount:
 2. A fungicidal mixture as claimed in claim 1 where the amidecompounds correspond to formula II-1

in which X¹ is CF₃ or halogen and X² is halogen.
 3. A fungicidal mixtureas claimed in claim 1, comprising, as amide compound of the formula II,the compound II-5.


4. A fungicidal mixture as claimed in claim 1, wherein the weight ratioof the triazolopyrimidine I to the amide compounds of the formula II isfrom 100:1 to 1:100.
 5. A fungicidal composition, comprising thefungicidal mixtures as claimed in claim 1 and a solid or liquid carrier.6. A method for controlling phytopathogenic harmful fungi, whichcomprises treating the harmful fungi, their habitat or the plants,seeds, soils, areas, materials or spaces to be kept free from them withthe triazolopyrimidine of the formula I as set forth in claim 1 andamide compounds of the formula II.
 7. A method as claimed in claim 6,wherein the triazolopyrimidine of the formula I and amide compounds ofthe formula II are applied simultaneously, that is either together orseparately, or in succession.
 8. A method as claimed in claim 6, whereinthe triazolopyrimidine of the formula I as is applied in an amount offrom 5 to 2000 g/ha.
 9. A method as claimed in claim 6, wherein theamide compounds of the formula II are applied in an amount of from 5 to2000 g/ha.
 10. The use of the compounds I and II as set forth in claim 1for preparing a composition suitable for controlling harmful fungi.